Keaction product anb process



@dteatedi Jan. 19, E93? ETE 'STTE REACTION PRODUCT PROCESS HermanAlexander Bruson and Lloyd W. Covert, Philadelphia, Pa, assignors toRiihms & Haas Copany, Padelphia, Pa.

No Drawing. Application October 27, 1934, Serial No. 750,278

9 Claims.

no-iz f n-on x1 wherein R is a nuclearly hydrogenated aromatichydrocarbon radical, and X and X each represent a hydrogen atom, alkylor hydroaromatic hydrocarbon radical, or jointly a polymethylene ring.

According to the present invention, the perhydro derivatives of,3,B-bis-(p-hydroxyphenyl)- propane, bis-(p-hydroxyphenyl)-methane,6,6,- bis- (p-hydroxy phenyl) -ethane, 1,1-bis- (p-hydroxyphenyl)cyclohexane, bis (,9 hydroxynaphtho) -methane,pap-bis(4-hydroxy-3-methylphenyl) -propane, and of similarly constitutedcompounds, when heated to temperatures above their melting point butbelow their critical cracking temperature, preferably in vacuo; andpreferably in the absence of inorganic dehydrating or dehydrogenatingcatalysts or of phenolic impurities gradually losetheir crystallinecharacteristics and go over into hard, transparent, glass-like resinshaving an extremely light color, (generally water white). These newresins are very resistant to alkalies, water, and dilute inorganicacids. They are in general soluble in alcohols such as butanol, butinsoluble in hydrocarbons. In physical properties these new resinsresemble natural dammar resin, giving low viscosity solutions whichdeposit fast-drying, low solvent retention films of good adhesion,gloss, and hardness.

- They can be used as resin ingredients in coating glass.

hydrides or mixtures thereof, whereby hard, brittle resins or semi-solidbalsam-like amorphous bodies are formed, which, depending upon thenature of the acids used, may be employed either in the manufacture ofoleo-resinous varnishes or as plasticizers for organic plasticmaterials.

The perhydro derivatives herein mentioned as the initial startingmaterials for resin manufacture are obtained by hydrogenating polyhydricphenols of the formula HO-R-C'i-R-OH is wherein R is an aromatichydrocarbon radical and X and X represent hydrogen, alkyl, aryl, orjointly a polymethylene ring; in the presence of an inert solvent suchas ethyl alcohol and an ,active hydrogenation catalyst such as finelydivided nickel at about 200 C. and about 150 atmospheres pressure untilthe aromatic groups R are both completely hydrogenated. The perhydroderivatives used are entirely free from partially hydrogenatedorunhydrogenated phenolic materials. This is ascertained by removing asample and testing for solubility in 10% potassium hydroxide solutionwhich dissolves such impurities but does not dissolve the perhydrocompound. The temperature of the hydrogenation should not be high enoughto crack the starting materials or the finished product; a temperaturerange of 190-220 C. being in general desirable. The catalyst is thenfiltered off and the solvent is removed by distillation from thephenol-free reaction product. The residue is the perhydro derivative. Itusually forms a colorless crystal mass.

This invention may be illustrated by the following examples, but theyare not to be considered as limiting the invention to the exactmaterials and conditions shown, since the invention may be otherwisepracticed within the scope of the appended claims:

Erample 1.-In practicing one embodiment of this invention,perhydro-[3,fi-[bis-(p-hydroxyphenyl) -propanel such as may be obtainedby hydrogenating the two benzene rings in 18,5- [bis(phydroxyphenyl)-propane] at 200 C. for 4 hours in its own weight of ethyl alcohol inthe presence of an active nickel catalyst until 12 atoms of hydrogenhave been taken up, was heated at 250-300 C. for 34 hours whilemaintaining 2 mm. pressure. About 20 grams of a colorless balsam-likematerial distilled off. The residue on cooling formed a colorless,transparent resin having a melting point of about 160 C. It may bedistilled in vacuo with slight decomposition, and boils at about 200C./2 mm. The vacuum distilled product melted at 130-150 C. and formed acolorless hard, brittle, glass solid. It was soluble in ethyl or butylalcohol.

In a similar manner, the perhydro derivatives of bis- (p-hydroxyphenyl)-methane HO CsH4-CH2-CsH4-OH, and of 6,6-bis-(p-hydroxyphenyl) -ethaneHO-CaHr-CH-CgHrOH H a yield colorless resins having similar propertieswhen heated to temperatures of from 250-350" C. The higher molecularhomologs such as the perhydro derivative of 1,1-bis-(p-hydroxyphenyl)cyclohexane HOCe 4C-CoH40H 3,0 CH3 Ha (1H9 likewise yield similarresins.

In practicing another embodiment of the present invention, the abovementioned perhydro dewith organic monocarboxylic or polycarboxylic acidsor with mixtures of monoand polycarboxylic acids, or anhydrides thereof.The condensation may be carried out by heating either in an inertorganic solvent under reflux under conditions whereby the water iscontinuously removed as fast as formed, or else in kettles fitted with ashort air condenser and preferably under constant agitation.

Among the acids which have been found suitable for condensation with theabove mentioned perhydro bodies are the fatty acids, particularlypropionic, crotomic, lactic, glycollic and alphahydroxyisobutyric. Otheracids such as oleic,

linoleic, stearic, elaeostearic, ricinoleic, or naphthenic can also beused. These latter condensation products are oily or soft somewhatviscous balsam-like masses which are soluble in ethyl acetate and can beused as plasticizers in coating compositions such as cellulose esters orcellulose ethers. By using rosin or polycarboxylic acids or anhydridessuch as phthalic, succinic, maleic or adipic, hard resins are obtainedupon heating to 190 -250 0., with the above mentioned perhydroderivatives. Esterification catalysts such as mineral acids, oxides, orsalts can be present during the condensation such as sulfuric, boric, orphosphoric acids, zinc or calcium oxides, or zinc chloride. oil, cottonseed oil, tung oil, castor oil, palm oil,

soya bean oil and the like may be added during the condensation in orderto modify the physical properties of the resins formed.

Example 2.--A mixture of 50 grams perhydro- ,6 9- [bis-(p-hydroxyphenyl) -propanel of melting point 192-193 C. and 60 gramspropionic anhydride was heated at 100 C. for 5-6 hours and then boiledone hour longer under reflux. The propionic acid was distilled oil andthe oily residue distilled in vacuo. It formed a very vis ous acetone,or butyl acetate and can be Fatty glycerides such as linseed colorlessoil boiling at 200-205 C./ 1.5 mm. This product was found to be anexcellent plasticizer for nitrocellulose, and cellulose acetate.

Example 3.A mixture of 50 grams perhydro- .flfi- [bis (p-hydroxyphenyl)-propane] 50 grams 85% lactic acid and 200 com. xylene was refluxed,while using an automatic water separator to continuously remove thewater as fast as formed and to return the xylene to the reaction vessel.When no more water came over (3-4 hours) the xylene solution of thereaction product obtained was cooled, washed thoroughly with water toremoveany free acidity, and the xylene distilled oil. The residue was apale yellow semi-solid,

The product obtained was a very paleambercolored, hard, brittle resinhaving a melting point 85-90 C. and acid number 7-8. It was readilysoluble in toluene. A varnish was prepared from the resin by heatingwith its own weight of Chinawood oil to-600 F. The clear varnishobtained was diluted with its own volume of petroleum naphtha, driersadded in the usual manner and a pale, fast drying varnish obtained. Byincreasing the amount of maleic anhydride to 60 grams and heating asabove for 6 hours,,a resin having a melting point Ill-130 C. wasobtained.

Example 5.-A mixture 0120 grams sebacic acid and 23.8 gramsperhydro-p,p-[bis-(phydroxyphenyD-propane] was heated in an open flaskat 190-195 C, for 5 hours at 190-200 C. A very tough, somewhat hardamber-colored resin was obtained. It was readily soluble in toluene,used in nitrocellulose lacquers as a gum.

Example 6.By using 14.8 grams phthalic anhydride in place of the sebacicacid in Example 5, and heating at 200 C. for '7 hours, a colorless, hardbrittle resin was obtained, which was readily soluble in butyl acetate,toluene, or warm tung oil.

It is already known that resins are obtained by heating polyhydricalcohols with polybasic acids such as phthalic, maleic, succimc, sebacicand the like. When dihydric alcohols are used in such prior process, lowmelting oily or waxy materials are invariably produced. According to thepresent invention, however, condensation products of perhydroderivatives of the type set forth herein with polybasic acids yieldshard, brittle, high melting resins which possess the unique property ofbeing readily soluble in hot drying or semi-drying oils in contrast tothe usual alkyd type resins which must first be heated with long-chainfatty acids or rosin in order to become oil-soluble.

The resinous materials that are obtained by" the heat treatment of theperhydro derivatives uct of perhydro- [bis-(p-hydroxyphenyl) -dimethylmethane] and a monocarboxylic acid.

4. A resin consisting of the condensation product of perhydro- [bis-(p-hydroxyphenyl) dimethyl methane] and lactic acid.

5. A resin consisting of a condensation product of a perhydro derivativeof a compound of the formula wherein R is an aromatic hydrocarbonnucleus, X and X represent hydrogen, alkyl, aryl, or jointly apolymethylene ring; and an organic monocarboxylic acid.

6. A process for preparing a resin or balsamlike material whichcomprises heating a perhydro derivative of a compound of the formulawherein R is an aromatic hydrocarbon nucleus, X and X representhydrogen, alkyl, aryl or jointly a polymethylene ring, with an organicmonocarboxylic acid.

7. A process of preparing a resin or balsamlike material which comprisesheating a perhydro derivative of a diarylol methane compound with anorganic monocarboxylic acid.

8. A resin consisting of the product obtainable by heating a perhydroderivative of a diarylol methane compound with an organic monocarboxylicacid.

9. A resin composition comprising a fatty glyceride and a condensationproduct obtainable by heating a perhydro derivative of a diarylolmethane compound with an organic monocarboxylic acid.

HERMAN ALEXANDER BRUSON. LLOYD W. COVERT.

